[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP1568669B1 - Silikoncarbid-poröser körper, verfahren zur herstellung desselben und wabenstruktur - Google Patents

Silikoncarbid-poröser körper, verfahren zur herstellung desselben und wabenstruktur Download PDF

Info

Publication number
EP1568669B1
EP1568669B1 EP03775840A EP03775840A EP1568669B1 EP 1568669 B1 EP1568669 B1 EP 1568669B1 EP 03775840 A EP03775840 A EP 03775840A EP 03775840 A EP03775840 A EP 03775840A EP 1568669 B1 EP1568669 B1 EP 1568669B1
Authority
EP
European Patent Office
Prior art keywords
silicon carbide
silicon
oxide phase
porous body
metallic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03775840A
Other languages
English (en)
French (fr)
Other versions
EP1568669A4 (de
EP1568669A1 (de
Inventor
Masahiro c/o NGK INSULATORS LTD. FURUKAWA
Nobuyuki c/o NGK INSULATORS LTD. TANAHASHI
Kenji c/o NGK INSULATORS LTD. MORIMOTO
Shinji c/o NGK INSULATORS LTD. KAWASAKI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Publication of EP1568669A1 publication Critical patent/EP1568669A1/de
Publication of EP1568669A4 publication Critical patent/EP1568669A4/de
Application granted granted Critical
Publication of EP1568669B1 publication Critical patent/EP1568669B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B01J35/57—Honeycombs
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/636—Polysaccharides or derivatives thereof
    • C04B35/6365—Cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0038—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by superficial sintering or bonding of particulate matter
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C04B2235/3481—Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C04B2235/728—Silicon content
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C04B2235/85—Intergranular or grain boundary phases
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24149—Honeycomb-like

Definitions

  • the present invention relates to a silicon carbide porous body, a process for producing the same, and a honeycomb structure.
  • the present invention relates to a silicon carbide porous body having high mechanical strength and preferably usable, for example, as a material constituting a filter, a catalyst carrier or the like for automobile exhaust gas purification, a process for producing the same, and a honeycomb structure comprising the silicon carbide porous body.
  • a porous honeycomb structure has been broadly used as a filter (diesel particulate filter (DPF)) for capturing/removing particulate matters included a soot-containing fluid such as a diesel engine exhaust gas, or a catalyst carrier for carrying catalyst components to purify toxic substances in the exhaust gas.
  • the honeycomb structure comprises: cell partition walls (ribs) forming a composite body of a plurality of adjacent cells; and a honeycomb outer wall which surrounds and holds outermost peripheral cells positioned in an outermost periphery of this cell composite body.
  • a silicon carbide porous body using fire-resistant silicon carbide particles as aggregates has been used as a material constituting the structure.
  • honeycomb-structure porous silicon carbide catalyst carrier which is obtained using impurity-containing silicon carbide having a predetermined specific surface area as a starting material.
  • the material is formed into a desired shape, dried, and thereafter fired in a temperature range of 1600 to 2200°C (see, e.g., JP-A-6-182228 ).
  • a sintering mechanism does not sufficiently function, therefore the growths of the neck portions are inhibited, and accordingly there has been a disadvantage that strength of the filter drops.
  • a porous honeycomb structure containing fire-resistant particles which are aggregates, especially silicon carbide and metallic silicon, and a process for producing the structure (see, e.g., JP-A-2002-201082 ).
  • a porous honeycomb structure can be inexpensively produced at a comparatively low firing temperature, and the obtained porous honeycomb structure has characteristics of being comparatively high in porosity, and high in thermal conductivity and strength.
  • DPF low porosity
  • a material having a higher porosity be used as a porous material constituting the filter.
  • DPF being provided with a regeneration system in which an oxidation catalyst is loaded on a conventional DPF (DPF for catalyst regeneration), and can oxidize to burn deposited particulates for continuously regeneration.
  • the DPF for regeneration the catalyst it is required to reduce the pressure loss of the filter as much as possible, and also required to make the porosity higher, concretely 50% or more, and especially around 70%.
  • the porosity of the silicon carbide porous body is raised, the strength accordingly drops.
  • a porosity of a certain or more degree for example, at a porosity of 60% or more, for example, there has been a problem that it is difficult to preferably use the porous body as a material constituting a filter, a catalyst carrier or the like for automobile exhaust gas purification.
  • EP-A-1375454 corresponding to W02002/081406 published 17 October 2002 , describes silicon carbide-based porous materials containing silicon carbide particles as an aggregate and metallic silicon. It is proposed to include an amorphous or crystalline silicate compound phase on or in the vicinity of the silicon carbide particles and/or the metallic silicon. In Example 4, strontium carbonate (1%) is included in the starting material of SiC and Si.
  • the present invention has been developed in view of the problems associated with the above-described conventional technique, and an object thereof is to provide a silicon carbide porous body having high mechanical strength and preferably usable, for example, as a material constituting a filter, a catalyst carrier or the like for automobile exhaust gas purification, a process for producing the same, and a honeycomb structure comprising the silicon carbide porous body.
  • the present invention provides the silicon carbide porous body as set out in claim 1.
  • the ratio of the total area of portions at which the silicon carbide particle and the oxide phase are brought into contact is in a range of 10 to 70% with respect to the total area of portions at which the silicon carbide particle, metallic silicon, and oxide phase are brought into contact.
  • the ratio of the total area of the portions with which the silicon carbide particle and the oxide phase are brought into contact is in a range of 25 to 50% with respect to the total area of the portions with which the silicon carbide particle, metallic silicon, and oxide phase are brought into contact.
  • the melting temperatures of the oxide phase is in a range of 1000 to 1400°C.
  • the melting viscosity of the oxide phase is lower tha, that of metallic silicon.
  • the ratio of mass of the oxide phase is in a range of 4.0 to 8.0 mass% with respect to a total mass of the silicon carbide particle and metallic silicon.
  • the invention also provides a honeycomb structure comprising: the silicon carbide porous body as set out in claim 1.
  • the invention further provides a process for producing a silicon carbide porous body, as set out in claim 9.
  • the amount of the compound to be added to the silicon carbide particles and metallic silicon and containing strontium, aluminum, and silicon, converted into the respective oxides (SrO, Al 2 O 3 , SiO 2 ), is set to a range of 4.0 to 8.0 parts by mass with respect to the total amount of 100 parts by mass of the silicon carbide particles and metallic silicon.
  • FIG. 1 is a sectional view schematically showing a silicon carbide porous body of the present embodiment.
  • silicon carbide particles 2 which are aggregates are bonded to metallic silicon 3 which is a bonding material in a state in which pores 4 are held between the silicon carbide particles 2, and/or between the silicon carbide particle 2 and metallic silicon 3 to constitute the silicon carbide porous body 1.
  • Oxide phases 5 containing oxides of silicon, aluminum, and alkaline earth metal are buried in at least some of fine pore portions 6 having a minimum distance of 10 ⁇ m or less between the surfaces of the silicon carbide particles 2, or between the surface of the silicon carbide particle 2 and that of metallic silicon 3 among the pores 4.
  • a ratio of a total (pore volumes of fine pore portions) of volumes of portions in which oxide phase 5 is not buried among the fine pore portions 6 is 20% or less with respect to a total (total pore volume) of volumes of portions in which any oxide phase 5 is not buried among the pores 4 including the fine pore portions 6.
  • the oxide phase 5 is buried to thereby thicken bonding between the silicon carbide particles 2 and/or between the silicon carbide particle 2 and metallic silicon 3, and the bonding is further secured. Consequently, the mechanical strength of the silicon carbide porous body 1 can be raised, and the porous body is preferably usable, for example, as a material constituting a filter, a catalyst carrier or the like for automobile exhaust gas purification.
  • the material can be sintered at a comparatively low firing temperature during production, producing costs are reduced, and producing yield is enhanced.
  • the silicon carbide particles 2 which are the aggregates are bonded to metallic silicon 3 which is the bonding material in a state in which the pores 4 are retained between the silicon carbide particles 2 and/or between the silicon carbide particle 2 and metallic silicon 3.
  • portions having a minimum distance of 10 ⁇ m or less between the surfaces of the silicon carbide particles 2, or between the surfaces of the silicon carbide particle 2 and metallic silicon 3 are the fine pore portions 6.
  • the oxide phases 5 are buried at least some of the fine pore portions 6. It is to be noted that the oxide phase 5 may be buried in such a manner as to seal all the fine pore portions 6.
  • a volume of the portion in which any oxide phase 5 is not buried in the pore 4 including the above-described fine pore portion 6, and that of the portion in which any oxide phase 5 is buried in the fine pore portion 6 can be calculated from a pore diameter distribution measured, for example, using a mercury porosimeter or the like.
  • the section of the silicon carbide porous body 1 is photographed by a scanning electron microscope (SEM) or the like, and images photographed in a plurality of sections are analyzed.
  • the volumes may be calculated as integrated values.
  • the above-described equation (1) is an evaluation method in which strength of bonding between the silicon carbide particles 2 is judged in a predetermined porosity.
  • the porosity e (%) and the contact length L (mm) per unit area (mm 2 ) satisfy the relation of the above-described equation (1), it can be judged that the silicon carbide porous body 1 has a superior strength as the constituting material of a DPF.
  • the silicon carbide porous body 1 constituting a sample is cut to obtain a predetermined cut face. At this time, to form the cut face into a uniformly flat face, the cut face may be appropriately polished.
  • a plane image obtained by photographing the cut face using the scanning electron microscope (SEM) or the like is taken into a calculator including a personal computer (PC) using image take-in means such as a scanner.
  • the taken-in plane image is divided and extracted as a specified silicon carbide particle portion originating from the silicon carbide particle 2, a specified metallic silicon portion originating from metallic silicon 3, a specified oxide phase portion originating from the oxide phase 5, and a specified portion (pore portion) originating from a portion in which any oxide phase 5 is not buried in the pore 4 including the fine pore portion 6.
  • a ratio of a total area of portions with which the silicon carbide particle 2 and the oxide phase 5 are brought into contact is preferably 10 to 70% with respect to a total area of portions with which the silicon carbide particle 2, metallic silicon 3, and oxide phase 5 are brought into contact.
  • the ratio of the area of the portions with which the silicon carbide particle 2 and oxide phase 5 are brought into contact is less than 10%, the mechanical strength of the silicon carbide porous body 1 cannot be sufficiently raised in some case.
  • the ratio of the area of the portion with which the silicon carbide particle 2 and oxide phase 5 are brought into contact exceeds 70%, there is fear that the silicon carbide particle 2 is brought into contact with metallic silicon 3 insufficiently, and thermal conductivity drops.
  • a total area of the portions with which the silicon carbide particle 2, metallic silicon 3, and oxide phase 5 are brought into contact, and a total area of the portions with which the silicon carbide particle 2 and oxide phase 5 are brought into contact can be calculated as integrated values.
  • a polished face of the silicon carbide porous body 1 is photographed using the scanning electron microscope (SEM) or the like, and images photographed in a plurality of sections in a thickness direction are subjected to computer image analysis.
  • a length (interface length) of the boundary line is extracted using an image analysis method similar to an evaluation method in which bonding strength is judged between the silicon carbide particles 2 in the above-described predetermined porosity, and the length is approximately usable.
  • the ratio of the total area of the portions with which the silicon carbide particle 2 and the oxide phase 5 are brought into contact is preferably 25 to 50% with respect to the total area of the portions with which the silicon carbide particle 2, metallic silicon 3, and oxide phase 5 are brought into contact.
  • the above-described alkaline earth metal is strontium.
  • the oxide phase 5 is amorphous and contains all oxides (SrO, Al 2 O 3 , SiO 2 ) of strontium, aluminum, and silicon, and a content ratio (SrO:Al 2 O 3 :SiO 2 ) of the respective oxides of strontium, aluminum, and silicon in the oxide phase 5 is (1.0:0.1:1.0) to (1.0:1.0:3.0) in accordance with each substance amount ratio (molar ratio).
  • the respective oxides are regarded as a ternary compound system, and an eutectic point is lowered. Accordingly, during firing, an oxide film is easily molten/removed with which the surface of the silicon carbide particle 2 and/or metallic silicon 3 is coated to obtain satisfactory wettability of metallic silicon 3, and a bonding portion for mutually bonding the silicon carbide particles 2 can further be thickened. It is to be noted that the oxide film with which the surface of the silicon carbide particle 2 and/or metallic silicon 3 is coated is SiO 2 or the like. Furthermore, when the eutectic point is lowered, viscosity of the oxide phase 5 can be lowered.
  • the oxide phase 5 can be buried in the fine pore portion 6 of the pore 4 in which metallic silicon 3 cannot be buried, and the mechanical strength of the silicon carbide porous body 1 can be enhanced in order to assist the bonding between the silicon carbide particles 2 by metallic silicon 3.
  • the substance amount ratio (molar ratio) of oxide (Al 2 O 3 ) of aluminum exceeds 1.0, a hardly soluble film is formed on the surface of metallic silicon 3, and the wettability between the silicon carbide particle 2 and metallic silicon 3 is deteriorated to lower the strength in some case.
  • the substance amount ratio (molar ratio) of oxide (SiO 2 ) of silicon is less than 1.0, or exceeds 3.0, the above-described eutectic point does not sufficiently drop, and the mechanical strength of the silicon carbide porous body 1 cannot be sufficiently effectively enhanced in some case.
  • the above-described "content ratio of the respective oxides of strontium, aluminum, and silicon in the oxide phase 5" can be calculated from values of Al, Sr and the like contained as impurities in the added compound and metallic silicon in terms of oxides, and a value of an amount of silicon dioxide (SiO 2 ) contained in the oxide film of the surface of the silicon carbide particle 2 and/or metallic silicon 3 in terms of an oxygen amount obtained by chemical analysis of a material powder.
  • melting temperatures of the above-described oxides are preferably 1000 to 1400°C.
  • the melting temperature is less than 1000°C, the viscosity of the oxide phase 5 excessively drops, and therefore the oxide phase 5 sometimes deviates in the silicon carbide porous body 1.
  • the melting temperature exceeds 1400°C, the viscosity of the oxide phase 5 does not sufficiently drop, and the oxide phase 5 does not easily enter the fine pore portion 6 of the pore 4 in some case.
  • melting viscosity of the oxide phase 5 is preferably lower than that of metallic silicon 3.
  • the oxide phase 5 more easily enters the fine pore portion 6 of the pore 4 of the silicon carbide porous body 1.
  • the ratio of mass of the oxide phase 5 is 1.0 to 10.0 mass% with respect to a total mass of the silicon carbide particle 2 and metallic silicon 3.
  • the mass ratio of the oxide phase 5 is less than 1.0 mass%, the strength of the silicon carbide porous body 1 cannot be sufficiently effectively enhanced.
  • the mass ratio of the oxide phase 5 exceeds 10.0 mass%, the amount of the oxide phase 5 is excessively large, therefore firing contraction is large, and the porosity of the silicon carbide porous body 1 drops.
  • the porous body is used as a filter such as DPF, pressure loss excessively increases in some case.
  • a ratio of mass of the oxide phase 5 is further preferably 4.0 to 8.0 mass% with respect to a total mass of the silicon carbide particle 2 and metallic silicon 3.
  • the honeycomb structure of the present embodiment comprises the silicon carbide porous body 1 (see FIG. 1 ) described above.
  • the honeycomb structure of the present embodiment reflects characteristics of the silicon carbide porous body 1 (see FIG. 1 ) which is a constituting material, and has superior resistances to oxidation, acid, particulate reaction, and thermal shock.
  • the honeycomb structure of the present embodiment is usable as a DPF, a DPF for regeneration by catalyst, catalyst carrier or the like under a high space velocity (SV) condition.
  • SV space velocity
  • the silicon carbide porous body of the present embodiment first, 1.0 to 10.0 parts by mass of compound containing strontium, aluminum, and silicon are added to silicon carbide particles and metallic silicon in terms of oxides (SrO, Al 2 O 3 , SiO 2 ) with respect to a total amount of 100 parts by mass of the silicon carbide particles and metallic silicon to obtain a raw material.
  • the compound containing strontium, aluminum, and silicon may contain only one type of alkaline earth metals (Mg, Ca, Sr, Ba) including strontium, aluminum, and silicon, or may contain a plurality of types.
  • the adding only one type of compound containing strontium, aluminum, and silicon may be added, or a plurality of types may be added in such a manner that the finally formed oxide phase contains at least one type of the alkaline earth metals, aluminum, and silicon.
  • the added amounts may be mutually different or equal.
  • a forming auxiliary agent such as an organic binder may be added if necessary.
  • the silicon carbide particle or metallic silicon sometimes contains a micro amount of impurities such as iron, aluminum, and calcium, but may be simply used, or may be subjected to chemical treatment such as chemical cleaning and refined for use.
  • aluminum is preferably contained in the form of aluminum oxide (Al 2 O 3 ) or metallic aluminum.
  • metallic aluminum may be contained as impurities of metallic silicon.
  • silicon is preferably contained in the form of silicon dioxide (SiO 2 ) or colloidal silica. It is to be noted that, in this case, silicon dioxide may be contained as an oxide film (SiO 2 ) with which the surface of the silicon carbide particle and/or metallic silicon is to be coated.
  • the raw materials obtained in this manner are mixed and kneaded to constitute a clay for forming, this clay is formed into a predetermined shape such as a honeycomb shape, this clay is calcined, and the organic binder is degreased to obtain a formed article.
  • the obtained formed article is fired, and an oxide phase containing the respective oxides of silicon, aluminum, and alkaline earth metal is buried in at least some of pores formed between the silicon carbide particles in such a manner that a ratio of a total volume (pore volume of the fine pore portion) of portions in which the oxide phase is not buried among the fine pore portions is 20% or less with respect to a total volume (total pore volume) of portions in which the oxide phase is not buried among the pores including the fine pore portions to obtain the porous body having a porous structure.
  • a type and/or an adding amount of the compound containing strontium, aluminum, and silicon are adjusted in such a manner that a content ratio (SrO:Al 2 O 3 :SiO 2 ) of the oxides of strontium, aluminum, and silicon is (1.0:0.1:1.0) to (1.0:1.0:3.0) in each substance amount ratio (molar ratio), the oxides being contained in the oxide phase constituting the porous body having the porous structure obtained by the firing.
  • the compound containing strontium, aluminum, and silicon, which has been added as the raw material, is decomposed or oxidized, and molten at the firing time.
  • the molten oxides of strontium, aluminum, and silicon are regarded as a ternary compound system, the eutectic point is lowered, and further viscosity is lowered. Accordingly, the oxide film on the surface of the silicon carbide particle and/or metallic silicon is molten/removed, the wettability of metallic silicon for bonding the silicon carbide particles is set to be satisfactory, and a bonding portion bonded to the silicon carbide particle can further be thickened.
  • the phase Since the viscosity of a surplus oxide phase drops, the phase easily enters the pores of the porous body, especially the fine pore portion having a small pore diameter. Since the phase solidifies in this state to aid the mutual bonding among the silicon carbide particles, the mechanical strength rises.
  • amount of the compound to be added to the silicon carbide particles and metallic silicon and containing strontium, aluminum, and silicon, converted into the respective oxides (SrO, Al 2 O 3 , SiO 2 ), is further preferably set to a range of 4.0 to 8.0 parts by mass with respect to a total amount of 100 parts by mass of the silicon carbide particles and metallic silicon.
  • calcining is preferably performed at a temperature lower than that at which metallic silicon melts.
  • a predetermined temperature may be once held at about 150 to 700°C, or a temperature rise speed may be delayed to 50°C/hr in a predetermined temperature range in performing the calcining.
  • a temperature level only or a plurality of temperature levels may be held depending on a type and amount of the used organic binder.
  • holding times may be equal to or different from one another.
  • the speed may be decreased only in one temperature segment or a plurality of segments. Further in a plurality of segments, the speeds may be equal to or different from one another.
  • metallic silicon needs to be softened at the firing time. Since melting point of metallic silicon is 1410°C, the firing temperature during the firing is preferably set to 1410°C or more. Furthermore, optimum firing temperature is determined by a micro structure or a characteristic value. However, since evaporation of metallic silicon proceeds at a temperature exceeding 1600°C, and the bonding via metallic silicon is difficult, the firing temperature is appropriately 1410 to 1600°C, preferably 1420 to 1580°C.
  • Silicon carbide particles having an average particle diameter of 33 ⁇ m, and powder of metallic silicon having an average particle diameter of 5 ⁇ m were blended in such a manner as to obtain a composition of 80:20 in a mass ratio, and a compound containing strontium oxide (SrO), aluminum oxide (Al 2 O 3 ), and silicon dioxide (SiO 2 ) was added to obtain a raw material.
  • a compound containing strontium oxide (SrO), aluminum oxide (Al 2 O 3 ), and silicon dioxide (SiO 2 ) was added to obtain a raw material.
  • 6 parts by mass of methyl cellulose, 2.5 parts by mass of surfactant, and 24 parts by mass of water were added as organic binders with respect to a total amount of 100 parts by mass of silicon carbide particles and metallic silicon, and the material was uniformly mixed and kneaded to obtain a forming clay.
  • the obtained clay was formed into a honeycomb shape having an outer diameter of 45 mm, length of 120 mm, partition wall thickness of 0.43 mm, and cell density of 100 cells/square inch (16 cells/cm 2 ) by an extruder.
  • firing was performed in a non-oxidizing atmosphere at 1450°C for two hours to prepare a honeycomb-structure silicon carbide porous body.
  • silicon carbide porous body silicon carbide particles and metallic silicon were bonded in a state in which pores were retained between the silicon carbide particles and/or between the silicon carbide particle and metallic silicon.
  • An oxide phase containing oxides of silicon, aluminum, and atmosphere was buried in at least some of fine pore portions having a minimum distance of 10 ⁇ m or less between the surfaces of the silicon carbide particles, or between the surfaces of the silicon carbide particle and metallic silicon among the pores.
  • Honeycomb-structure silicon carbide porous bodies (Example 3 and Comparative Example 7) were prepared by operations similar to those of Examples 1 and 2, Comparative Examples 1 to 6 described above except that 10 parts by mass of foaming resin (acrylonitrile-based plastic balloons (average particle diameter of 50 ⁇ m)), and 15 parts by mass of organic pore former (starch (average particle diameter of 50 ⁇ m)) were added in addition to a compound containing strontium oxide (SrO) which was an alkaline earth metal, aluminum oxide (Al 2 O 3 ), and silicon dioxide (SiO 2 ).
  • foaming resin acrylonitrile-based plastic balloons (average particle diameter of 50 ⁇ m)
  • starch average particle diameter of 50 ⁇ m
  • SiO 2 silicon dioxide
  • a ratio (%) (hereinafter referred to sometimes as micro porosity (%)) of a total volume (pore volume of fine pore portion) of portions (having pre diameters of 10 ⁇ m or less) was calculated in which any oxide phase was not buried among the fine pore portions having a minimum distance of 10 ⁇ m or less between the surfaces of the silicon carbide particles, or between the surfaces of the silicon carbide particle and metallic silicon, with respect to a total volume (total pore volume) of portions in which any oxide phase was not buried among pores including the above-described fine pore portions, using a pore diameter distribution measured by a mercury porosimeter. Results are shown in Table 1.
  • Example 1 1.0 : 0.2 : 2.0 1.7 17 46 11 45 25
  • Example 2 1.0 : 0.2 : 1.3 4.1 8 59 35 44 40
  • Example 3 1.0 : 0.2 : 2.1 5.8 9 48 38 59 18
  • ratios were calculated: each substance amount ratio (molar ratio) (SrO:Al 2 O 3 :SiO 2 ) of oxides of strontium, aluminum, and silicon in the oxide phase constituting each prepared silicon carbide porous body; and a ratio (mass%) (hereinafter referred to simply as the ratio (mass%) of the mass of the oxide phase in some case) of the mass of the oxide phase with respect to a total mass of the silicon carbide particles which were aggregates and metallic silicon which was a bonding material.
  • the ratios were calculated from an added compound and a compound contained as impurities in the silicon carbide particles or silicon carbide particle material. Results are shown in Table 1.
  • values may be calculated, when measuring and quantifying a characteristic X-ray inherent in each element (Sr, Al, Si, O) by EDS point analysis in the oxide phase existing in a polished face of the prepared silicon carbide porous body.
  • the values may be calculated by quantification by predetermined chemical analysis or the like, but the measuring method is not limited to the above-described method.
  • each silicon carbide porous body was analyzed using application (Image-Pro Plus (trade name) (manufactured by MEDIA CYBERNETICS Co.) for image analysis. Specifically, first the silicon carbide porous body constituting a sample was cut to obtain a predetermined cut face. At this time, to form the cut face into a uniformly flat face, the cut face may be appropriately polished. A plane image obtained by photographing the cut face using the scanning electron microscope (SEM) or the like was taken into a calculator including a personal computer (PC) using image take-in means such as a scanner.
  • SEM scanning electron microscope
  • PC personal computer
  • the taken-in plane image was divided and extracted as the silicon carbide particle 2, metallic silicon 3, oxide phase 5, and portion (pore portion) in which any oxide phase 5 was not buried in the pore 4 including the fine pore portion 6 as shown in FIG. 1 .
  • a predetermined image processing method was applied to a boundary among the extracted silicon carbide particle 2, metallic silicon 3, and oxide phase 5, a boundary line having a width for one pixel was extracted, and the total of the lengths per unit area (1 mm 2 ) was calculated as the contact length L (mm/mm 2 ). Obtained results are shown in Table 1.
  • a graph in which the contact length L (mm/mm 2 ) is plotted with respect to the value of the porosity ⁇ (%) is shown in FIG. 2 . It is to be noted that a straight line in FIG. 2 was drawn based on a lower-limit value of the following equation (1): L ⁇ - 1.0 ⁇ ⁇ + 90
  • a ratio (%) (hereinafter sometimes referred to as the oxide bonding ratio (%)) of a total area of portions with which the silicon carbide particles and oxide phase were brought into contact was calculated with respect to a total area of portions with which the silicon carbide particles, metallic silicon, and oxide phase were brought into contact by computer image analysis of the cut face of the silicon carbide porous body photographed using a scanning electron microscope (SEM) or the like.
  • SEM scanning electron microscope
  • a length (interface length) of a boundary line between the silicon carbide particle and metallic silicon, and that (interface length) of the boundary line between the silicon carbide particle and oxide phase were calculated using an image analysis method similar to the above-described image analysis method.
  • a ratio of a total interface length between the silicon carbide particle and the oxide phase was calculated with respect to a total interface length of the silicon carbide particle with respect to metallic silicon and oxide phase to obtain an oxide phase bonding ratio. Results are shown in Table 1.
  • An electron microscope photograph of the silicon carbide porous body of Example 1 is shown in FIG. 3
  • an electron microscope photograph of the silicon carbide porous body of Example 2 is shown in FIG. 4 .
  • Image-Pro Plus trade name
  • Example 2 since the ratio of the oxide phase was 4.1% and further large, and the micro porosity was 8%, the effect was sufficient (oxide bonding ratio: 35%) that the bonding between the silicon carbide particles and/or between the silicon carbide particle and metallic silicon was reinforced by the oxide phase, and the strength was 40 MPa and superior.
  • Comparative Example 5 in which the ratio of silicon dioxide (SiO 2 ) is 0.5 in each substance amount ratio (molar ratio) of oxide, the eutectic point of the oxide phase could not be sufficiently lowered, and it was not possible to sufficiently lower the viscosity of a molten compound, or an oxide film with which the surface of the silicon carbide particle and/or metallic silicon was coated. Therefore, the wettability of metallic silicon was bad, further the molten oxide phase could not sufficiently enter between the silicon carbide particles and/or between the silicon carbide particle and metallic silicon, and the strength of the silicon carbide porous body was only 16 MPa.
  • Example 3 in which the porosity was similarly enhanced, as compared with Comparative Example 7, the ratio of the oxide phase was 5.8% and very large, and the micro porosity was 9%. Therefore, since the effect was sufficient (oxide bonding ratio: 38%) that the bonding was strengthened between the silicon carbide particles and/or between the silicon carbide particle and metallic silicon by the oxide phase. Therefore, although the porosity was 59% and very high, the strength was 18 MPa, and remarkably superior, and the example was usable, for example, as the material constituting the filter, catalyst carrier or the like for the automobile exhaust gas purification.
  • Examples 1 to 3 have superior strengths as the constituting materials of the DPF in order to sufficiently satisfy the equation (1).
  • a silicon carbide porous body of the present invention and a honeycomb structure comprising the silicon carbide porous body have high mechanical strength, and are preferably usable as materials constituting a filter, a catalyst carrier or the like for automobile exhaust gas purification.
  • a process for producing the silicon carbide porous body of the present invention is capable of simply and inexpensively producing the silicon carbide porous body.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Filtering Materials (AREA)
  • Catalysts (AREA)
  • Ceramic Products (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
  • Exhaust Gas After Treatment (AREA)

Claims (10)

  1. Poröser Siliciumcarbidkörper, der Siliciumcarbidteilchen, die Aggregate sind, und metallisches Silicium, das ein Bindematerial ist, derart miteinander verbunden umfasst, dass Poren (4) zwischen den Siliciumcarbidteilchen und/oder zwischen dem Siliciumcarbidteilchen und dem metallischen Silicium verbleiben,
    dadurch gekennzeichnet, dass eine amorphe Oxidphase (5), die Oxide von Strontium, Aluminium und Silicium (SrO : Al2O3 : SiO2) im Verhältnis (1,0 : 0,1 : 1,0) bis (1,0 : 1,0 : 3,0) im Sinne des Mengenverhältnisses (Molverhältnisses) jeder Substanz enthält, zumindest in manchen der feinporigen Abschnitte (6) der Poren verborgen ist, wobei die feinporigen Abschnitte einen Abstand von 10 µm oder weniger zwischen den Oberflächen der Siliciumcarbidteilchen oder zwischen den Oberflächen des Siliciumcarbidteilchens und metallischem Silicium aufweisen,
    dass die Menge der Oxidphase (5) 1,0 bis 10 Massen-%, bezogen auf die Gesamtmasse der Siliciumcarbidteilchen und des metallischen Siliciums, beträgt und
    dass das Gesamtporenvolumen von Abschnitten dieser feinporigen Abschnitte (6), in denen die Oxidphase (5) nicht verborgen ist, 20 % oder weniger, bezogen auf das Gesamtporenvolumen der Abschnitte der Poren (4), in denen die Oxidphase (5) nicht verborgen ist, beträgt.
  2. Poröser Siliciumcarbidkörper nach Anspruch 1, worin ein ebenes Bild, das durch das Photographieren einer Schnittfläche des porösen Siliciumcarbidkörpers, geschnitten mit einer vorbestimmten Ebene, erhalten wurde, einem Bildanalyseverfahren unterzogen und in einen bestimmten Porenabschnitt, der von dem Abschnitt stammt, in dem die Oxidphase nicht in der Pore verborgen ist, einschließlich des feinporigen Abschnitts, einen bestimmten Siliciumcarbidteilchenabschnitt, der von dem Siliciumcarbidteilchen stammt, einen bestimmten metallischen Siliciumabschnitt, der von metallischem Silicium stammt, und einen bestimmten Oxidphasenabschnitt, der von der Oxidphase stammt, unterteilt wird und ein Verhältnis der folgenden Gleichung (1) durch eine Gesamtlänge (Kontaktlänge) L (mm) pro Einheitsfläche (1 mm2) eines Abschnitts, mit dem der Siliciumcarbidteilchenabschnitt, der metallische Siliciumabschnitt und der Oxidphasenabschnitt auf dem geteilten ebenen Bild in Kontakt gebracht werden, und einer Porosität ε (%) des porösen Siliciumcarbidkörpers erfüllt wird: L ≥ - 1 , 0 ⁢ ε + 90
    Figure imgb0005
  3. Poröser Siliciumcarbidkörper nach Anspruch 1 oder 2, worin das Verhältnis der Gesamtfläche der Abschnitte, an der das Siliciumcarbidteilchen und die Oxidphase in Kontakt sind, in einem Bereich von 10 bis 70 %, bezogen auf die Gesamtfläche der Abschnitte, an der das Siliciumcarbidteilchen, das metallische Silicium und die Oxidphase in Kontakt sind, liegt.
  4. Poröser Siliciumcarbidkörper nach Anspruch 3, worin das Verhältnis der Gesamtfläche der Abschnitte, mit denen das Siliciumcarbidteilchen und die Oxidphase in Kontakt gebracht werden, in einem Bereich von 25 bis 50 %, bezogen auf die Gesamtfläche der Abschnitte, mit denen das Siliciumcarbidteilchen, das metallische Silicium und die Oxidphase in Kontakt gebracht werden, liegt.
  5. Poröser Siliciumcarbidkörper nach Anspruch 1, worin die Schmelztemperatur der Oxidphase (SrO, Al2O3, SiO2) im Bereich von 1000 bis 1400 °C liegt.
  6. Poröser Siliciumcarbidkörper nach Anspruch 5, worin die Schmelzviskosität der Oxidphase geringer ist als jene des metallischen Siliciums.
  7. Poröser Siliciumcarbidkörper nach Anspruch 5 oder Anspruch 6, worin das Massenverhältnis der Oxidphase im Bereich von 4,0 bis 8,0 Massen-%, bezogen auf die Gesamtmasse des Siliciumcarbidteilchens und metallischen Siliciums, liegt.
  8. Wabenstruktur, die einen porösen Siliciumcarbidkörper nach einem der Ansprüche 1 bis 7 umfasst.
  9. Verfahren zur Herstellung eines porösen Siliciumcarbidkörpers nach Anspruch 1 mit den folgenden Schritten: dem Zusetzen einer Verbindung, die Strontium, Aluminium und Silicium im Bereich von 1,0 bis 10,0 Massenteilen im Sinne von Oxiden (SrO, Al2O3, SiO2), bezogen auf insgesamt 100 Massenteile von Siliciumcarbidteilchen und metallischem Silicium, enthält, zu Siliciumcarbidteilchen und metallischem Silicium durch Anpassen von Art und/oder zugesetzter Menge der Verbindung, die Strontium, Aluminium und Silicium enthält, in einer Weise, sodass ein Gehaltsverhältnis (SrO : Al2O3 : SiO2) der in einer amorphen Oxidphase, die zumindest einen Abschnitt des porösen Körpers mit der durch das Brennen erhaltenen porösen Struktur ausmacht, enthaltenen Oxide von Strontium, Aluminium und Silicium im Bereich von (1,0 : 0,1 : 1,0) bis (1,0 : 1,0 : 3,0) im Sinne des Mengenverhältnisses (Molverhältnisses) jeder Substanz liegt, um ein Rohmaterial zu erhalten, dem Formen des erhaltenen Rohmaterials zu einer vorbestimmten Gestalt, um einen Formteil zu erhalten, dem Entfetten und anschließenden Brennen des erhaltenen Formteils, um den porösen Körper zu erhalten, wodurch eine verborgene amorphe Oxidphase (5) gebildet wird, die die jeweiligen Oxide von Strontium, Aluminium und Silicium enthält und zumindest in manchen der feinporigen Abschnitte (6) mit einem Abstand von 10 µm oder weniger zwischen den Oberflächen der jeweiligen Siliciumcarbidteilchen oder zwischen den Oberflächen des Siliciumcarbidteilchens und dem metallischen Silicium unter den zwischen den Siliciumcarbidteilchen gebildeten Poren (4) vorhanden ist, wobei das Gesamtvolumen von Abschnitten der feinporigen Abschnitte (6), in denen die Oxidphase nicht verborgen ist, 20 % oder weniger, bezogen auf das Gesamtporenvolumen von Abschnitt der Poren (4), in denen die Oxidphase nicht verborgen ist, ausmacht.
  10. Verfahren zur Herstellung eines porösen Siliciumcarbidkörpers nach Anspruch 9, worin die zu den Siliciumcarbidteilchen und dem metallischen Silicium zuzusetzende Menge der Verbindung, die Strontium, Aluminium und Silicium enthält, überführt in die jeweiligen Oxide (SrO, Al2O3, SiO2), im Bereich von 4,0 bis 8,0 Massenteilen, bezogen auf die Gesamtmenge von 100 Massenteilen der Siliciumcarbidteilchen und des metallischen Siliciums, liegt.
EP03775840A 2002-11-20 2003-11-19 Silikoncarbid-poröser körper, verfahren zur herstellung desselben und wabenstruktur Expired - Lifetime EP1568669B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2002336142 2002-11-20
JP2002336142 2002-11-20
PCT/JP2003/014726 WO2004046063A1 (ja) 2002-11-20 2003-11-19 炭化珪素質多孔体及びその製造方法、並びにハニカム構造体

Publications (3)

Publication Number Publication Date
EP1568669A1 EP1568669A1 (de) 2005-08-31
EP1568669A4 EP1568669A4 (de) 2009-03-04
EP1568669B1 true EP1568669B1 (de) 2012-09-05

Family

ID=32321794

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03775840A Expired - Lifetime EP1568669B1 (de) 2002-11-20 2003-11-19 Silikoncarbid-poröser körper, verfahren zur herstellung desselben und wabenstruktur

Country Status (7)

Country Link
US (1) US7244685B2 (de)
EP (1) EP1568669B1 (de)
JP (1) JP4426459B2 (de)
KR (1) KR100649476B1 (de)
AU (1) AU2003284416A1 (de)
PL (1) PL214868B1 (de)
WO (1) WO2004046063A1 (de)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7452591B2 (en) * 2002-03-29 2008-11-18 Ngk Insulators, Ltd. Silicon carbide based porous material and method for production thereof
JP4394343B2 (ja) * 2002-12-11 2010-01-06 日本碍子株式会社 炭化珪素質多孔体及びその製造方法、並びにハニカム構造体
FR2894028B1 (fr) 2005-11-30 2008-07-11 Saint Gobain Ct Recherches Methode de selection d'une structure de filtration d'un gaz
JP4863904B2 (ja) 2006-03-31 2012-01-25 イビデン株式会社 ハニカム構造体およびその製造方法
WO2008114895A1 (en) * 2007-03-22 2008-09-25 Posco Silicon carbide-based porous body and method of fabricating the same
US8620059B2 (en) 2007-12-13 2013-12-31 Fpinnovations Characterizing wood furnish by edge pixelated imaging
KR101133650B1 (ko) * 2009-11-04 2012-04-10 한국에너지기술연구원 뮬라이트 결합 탄화규소질 고온가스필터 제조방법
KR101118607B1 (ko) 2010-08-19 2012-02-27 한국에너지기술연구원 스트론튬 카보네이트를 포함하는 고온 집진필터제조용 탄화규소 세라믹 조성물 및 그 제조방법
JP5875997B2 (ja) * 2012-03-22 2016-03-02 日本碍子株式会社 ハニカム構造体及びハニカム構造体の製造方法
JP6006782B2 (ja) 2012-03-28 2016-10-12 日本碍子株式会社 多孔質材料及びハニカム構造体
WO2013186922A1 (ja) 2012-06-15 2013-12-19 イビデン株式会社 ハニカムフィルタ
WO2013186923A1 (ja) 2012-06-15 2013-12-19 イビデン株式会社 ハニカムフィルタ
WO2014054159A1 (ja) 2012-10-04 2014-04-10 イビデン株式会社 ハニカムフィルタ
GB2509115A (en) * 2012-12-20 2014-06-25 Daimler Ag Particulate filter soaked in acid
JP5883410B2 (ja) * 2013-03-29 2016-03-15 日本碍子株式会社 ハニカム構造体の製造方法
JP6239305B2 (ja) 2013-07-31 2017-11-29 イビデン株式会社 ハニカムフィルタ
JP6239303B2 (ja) * 2013-07-31 2017-11-29 イビデン株式会社 ハニカムフィルタ
JP6239306B2 (ja) * 2013-07-31 2017-11-29 イビデン株式会社 ハニカムフィルタ
JP6239304B2 (ja) 2013-07-31 2017-11-29 イビデン株式会社 ハニカムフィルタ
JP6239307B2 (ja) 2013-07-31 2017-11-29 イビデン株式会社 ハニカムフィルタ
JP6285225B2 (ja) 2014-03-12 2018-02-28 日本碍子株式会社 ハニカム構造体
US9487448B2 (en) 2014-03-18 2016-11-08 Ngk Insulators, Ltd. Honeycomb structure
JP6654085B2 (ja) * 2016-03-31 2020-02-26 日本碍子株式会社 多孔質材料、及び多孔質材料の製造方法並びにハニカム構造体
JP6788515B2 (ja) * 2017-02-02 2020-11-25 日本碍子株式会社 目封止ハニカム構造体
JP6906468B2 (ja) * 2018-03-30 2021-07-21 日本碍子株式会社 セラミックス多孔体及びその製造方法、並びに集塵用フィルタ
JP7325473B2 (ja) * 2021-03-30 2023-08-14 日本碍子株式会社 多孔質ハニカム構造体及びその製造方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4946487A (en) * 1988-11-14 1990-08-07 Norton Company High temperature filter
JPH0665628B2 (ja) * 1989-10-06 1994-08-24 イーグル工業株式会社 多孔質炭化珪素質材料の製造方法
JPH0813706B2 (ja) * 1991-07-02 1996-02-14 工業技術院長 炭化珪素／金属珪素複合体及びその製造方法
JP3548914B2 (ja) * 1992-12-16 2004-08-04 イビデン株式会社 触媒担体の製造方法
JP4136319B2 (ja) * 2000-04-14 2008-08-20 日本碍子株式会社 ハニカム構造体及びその製造方法
JP4426083B2 (ja) * 2000-11-17 2010-03-03 日本碍子株式会社 炭化珪素質多孔体及びその製造方法
JP2002154876A (ja) * 2000-11-17 2002-05-28 Ngk Insulators Ltd ハニカム構造体及びその製造方法
JP4307781B2 (ja) * 2001-03-30 2009-08-05 日本碍子株式会社 炭化珪素質多孔体及びその製造方法
US7452591B2 (en) * 2002-03-29 2008-11-18 Ngk Insulators, Ltd. Silicon carbide based porous material and method for production thereof
JP4394343B2 (ja) * 2002-12-11 2010-01-06 日本碍子株式会社 炭化珪素質多孔体及びその製造方法、並びにハニカム構造体

Also Published As

Publication number Publication date
PL214868B1 (pl) 2013-09-30
EP1568669A4 (de) 2009-03-04
US7244685B2 (en) 2007-07-17
KR100649476B1 (ko) 2006-11-28
JP4426459B2 (ja) 2010-03-03
JPWO2004046063A1 (ja) 2006-03-16
PL377069A1 (pl) 2006-01-23
WO2004046063A1 (ja) 2004-06-03
AU2003284416A1 (en) 2004-06-15
EP1568669A1 (de) 2005-08-31
US20060029768A1 (en) 2006-02-09
KR20050083959A (ko) 2005-08-26

Similar Documents

Publication Publication Date Title
EP1568669B1 (de) Silikoncarbid-poröser körper, verfahren zur herstellung desselben und wabenstruktur
EP1493724B1 (de) Poröses material und herstellungsverfahren dafür
JP4307781B2 (ja) 炭化珪素質多孔体及びその製造方法
EP1277714B1 (de) Wabenförmige struktur und verfahren zur herstellung derselben
EP1600432B1 (de) Poröses material auf siliziumkarbidbasis, herstellungsverfahren dafür und wabenstruktur
EP1364928B1 (de) Wabenförmige struktur
EP1364930B1 (de) Wabenförmige struktur und verfahren zur herstellung derselben
EP2671857B1 (de) Wabenstruktur aus siliciumcarbidmaterial, und katalysatorträger für elektrische erhitzung
KR20020037040A (ko) 뮬라이트체 및 뮬라이트체의 형성방법
WO2003082773A1 (en) Mullite bodies and methods of forming mullite bodies
EP2957548B1 (de) Wabenstruktur
ZA200206263B (en) Honeycomb structure and method for manufacture thereof.
US10882796B2 (en) Ceramic porous body and method for producing the same, and dust collecting filter
CN116669830B (zh) 碳化硅陶瓷蜂窝状结构体及其制造方法
JP2005047796A (ja) 窒化ケイ素質フィルタの製造法
ZA200209674B (en) Silicon Carbide based porous article and method for preparation thereof.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050609

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RBV Designated contracting states (corrected)

Designated state(s): DE FR

A4 Supplementary search report drawn up and despatched

Effective date: 20090203

17Q First examination report despatched

Effective date: 20110222

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60342036

Country of ref document: DE

Effective date: 20121031

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20130606

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60342036

Country of ref document: DE

Effective date: 20130606

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20191014

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201130

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20210929

Year of fee payment: 19

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60342036

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230601